Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2009 Aug 26;131(33):11707-11.
doi: 10.1021/ja9054959.

Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs

Grant T Rice  1 , M Christina White
Affiliations

Allylic C-H amination for the preparation of syn-1,3-amino alcohol motifs

Grant T Rice et al. J Am Chem Soc. .

Abstract

A highly selective and general Pd/sulfoxide-catalyzed allylic C-H amination reaction en route to syn-1,3-amino alcohol motifs is reported. Key to achieving this reactivity under mild conditions is the use of electron-deficient N-nosyl carbamate nucleophiles that are thought to promote functionalization by furnishing higher concentrations of anionic species in situ. The reaction is shown to be orthogonal to classical C-C bond-forming/-reduction sequences as well as nitrene-based C-H amination methods.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Design Principles for Intramolecular C—H Amination
Scheme 1
Scheme 1
Origin of Diastereoselectivity a1 (10 mol%), 1,2-bis(phenylsulfinyl)ethane (5 mol%), p-nitrobenzoic acid (10 mol%), phenyl benzoquinone (2 equiv.), oxygenated DCE (0.66 M), 45°C. 24 h. bIsolated yield of major syn- product. cdr of crude reaction.
Scheme 2
Scheme 2
Total Synthesis of (+)-allosedridine (a) NsNCO (1.1 equiv.), THF, r.t. (93%); (b) standard conditions; (c) Isolated yield of major syn- product; (d) PhSH (1.2 equiv.), K2CO3 (3 equiv.), DMF, 0°C, 4 h (91%); (e) n-BuLi (1.0 equiv.), THF, -78°C; but-3-enyl trifluoromethanesulfonate (1.2 equiv.), -78°C to 0°C, 2 h (89%); (f) Grubbs (II) (8 mol%), toluene, 65°C, 3 h; H2, Pd-C, MeOH, r.t., 2 h (80%); (g) KOH/EtOH (1.7 M), 45°C, 2 h (73%).
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. List B. J Am Chem Soc. 2000;122:9336.
    2. Wenzel AG, Jacobsen EN. J Am Chem Soc. 2002;124:12964. - PubMed
    3. Kochi T, Tang TP, Ellman JA. J Am Chem Soc. 2003;125:11276. - PubMed
    4. Matsunaga S, Yoshida T, Morimoto H, Kumagai N, Shibasaki M. J Am Chem Soc. 2004;126:8777. - PubMed
    5. Josephsohn NS, Snapper ML, Hoveyda AH. J Am Chem Soc. 2004;126:3734. - PubMed
    6. Enders D, Grondal C, Vrettou M, Raabe G. Angew Chem Int Ed. 2005;44:4079. - PubMed

    1. For some recent examples of asymmetric conjugate addition reactions with nitrogen nucleophiles to furnish β-amino ketones see: Myers JK, Jacobsen EN. J Am Chem Soc. 1999;121:8959.Guerin DJ, Miller SJ. J Am Chem Soc. 2002;124:2134.Sibi MP, Prabagaran N, Ghorpade SG, Jasperse CP. J Am Chem Soc. 2003;125:11796.Yamigawa N, Qin H, Matsunaga S, Shibasaki M. J Am Chem Soc. 2005;127:13419.Chen YK, Yoshida M, MacMillan DWC. J Am Chem Soc. 2006;128:9328.

    1. Espino CG, Wehn PM, Chow J, Du Bois J. J Am Chem Soc. 2001;123:6935.Fiori KW, Fleming JJ, Du Bois J. Angew Chem Int Ed. 2004;43:4349.A sulfamate product analogous to 4 was generated via a chemoselective Rh-nitrene based reaction in 43% yield: Zalatan DN, Du Bois J. J Am Chem Soc. 2008;130:9220.Milczek E, Boudet N, Blakey S. Angew Chem Int Ed. 2008;47:6825.Liang JL, Yuan SX, Huang JS, Yu WY, Che CM. Angew Chem Int Ed. 2002;41:3465.

    1. Interestingly, high chemoselectivities and reactivities have been reported for intermolecular Rh-nitrene allylic aminations of internal olefins: Liang C, Collet F, Robert-Peillard F, Müller P, Dodd RH, Dauban P. J Am Chem Soc. 2008;130:343.

    1. Linear allylic C—H acetoxylation: Chen MS, White MC. J Am Chem Soc. 2004;126:1346.Branched allylic C—H esterification: Chen MS, Prabagaran N, Labenz NA, White MC. J Am Chem Soc. 2005;127:6970.Oxidative C—H macrolactonization: Fraunhoffer KJ, Prabagaran N, Sirois LE, White MC. J Am Chem Soc. 2006;128:9032.For a linear allylic acetoxylation reaction using DMA solvent see: Mistudome T, Umetani T, Nosaka N, Mori K, Mizugaki T, Ebitani K, Kaneda K. Angew Chem Int Ed. 2006;45:481.

Publication types